ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSK..HRIS..MTNORS..SM..................JBDM Ver 0.1.63 (23 May 2017) - 2100000/03118263EUROPEAN PATENT SPECIFICATIONB120180725EP15762201.02015031020160929jaenen201404731420140311JP20180725201830201701182017032018072520183020180618C08L 101/00 20060101AFI20180102BHEP C07C 31/38 20060101ALI20180102BHEP C07C 43/13 20060101ALI20180102BHEP C07F 5/02 20060101ALI20180102BHEP C08K 5/55 20060101ALI20180102BHEP C09D 201/00 20060101ALI20180102BHEP C09K 3/18 20060101ALI20180102BHEP C03C 17/00 20060101ALI20180102BHEP deVERBUNDSTOFFMATERIAL AUS HARZFLUORHALTIGEN BORSÄUREVERBUNDTEILCHENenCOMPOSITE MATERIAL OF RESIN-FLUORINE-CONTAINING BORIC ACID COMPOSITE PARTICLESfrMATÉRIAU COMPOSITE DE PARTICULES COMPOSITES DE RÉSINE ET D'ACIDE BORIQUE CONTENANT DU FLUORJP-A- 2002 348 567JP-A- 2003 534 439JP-A- 2011 505 423JP-A- 2014 196 482RACHEL M. LANIGAN ET AL: "Direct Synthesis of Amides from Carboxylic Acids and Amines Using B(OCH 2 CF 3 ) 3", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 78, no. 9, 3 May 2013 (2013-05-03), pages 4512-4523, XP055394847, US ISSN: 0022-3263, DOI: 10.1021/jo400509nMICHAEL A. BECKETT ET AL: "Lewis Acidity in Haloalkyl Orthoborate and Metaborate Esters", PHOSPHORUS, SULFUR AND SILICON AND THE RELATED ELEMENTS, vol. 169, no. 1, 1 January 2001 (2001-01-01), pages 113-116, XP055394850, US ISSN: 1042-6507, DOI: 10.1080/1042650010854660320171017FUKUSHIMA, Takeshic/o UNIMATEC CO. LTD. 831-2 Kamishoda IsoharamachiKitaibaraki-shi Ibaraki 319-1544JPSATO, Katsuyukic/o UNIMATEC CO. LTD. 831-2 Kamishoda IsoharamachiKitaibaraki-shi Ibaraki 319-1544JPSAWADA, Hideoc/o HIROSAKI UNIVERSITY 1 Bunkyo-choHirosaki-shi Aomori 036-8224JPUnimatec Co., Ltd.10135009231006EP/cf12-15, Shibadaimon 1-chome Minato-kuTokyo 105-0012JPHirosaki University10154940631006EP/cf1, Bunkyo-choHirosaki-shi, Aomori 036-8224JPBeckmann, Clauset al100057330Kraus & Weisert Patentanwälte PartGmbB Thomas-Wimmer-Ring 1580539 MünchenDEALATBEBGCHCYCZDEDKEEESFIFRGBGRHRHUIEISITLILTLULVMCMKMTNLNOPLPTRORSSESISKSMTRJP201505702320150310jaWO201513734420150917201537 TECHNICAL FIELD

The present invention relates to a composite material of resin - fluorine-containing boric acid composite particles. More particularly, the present invention relates to a composite material of resin - fluorine-containing boric acid composite particles, which has improved surface-treatment characteristics.

BACKGROUND ART

It is known that various surface characteristics are exhibited by coating inorganic material surfaces with various compounds or polymers. In particular, when a fluorine-based compound is used for surface treatment, surface modification can be applied for not only water-repellency, but also oil-repellency, due to properties of fluorine atoms. Thus, such fluorine-based compounds are used for coating on various substrates.

In particular, highly water- and oil-repellent coatings can be obtained by applying a surface-treating agent having a C8-perfluoroalkyl group to substrates. However, it is recently reported that compounds containing a perfluoroalkyl group having 7 or more carbon atoms induce intracellular communication inhibition, which is considered to be a carcinogenic factor, in in-vitro tests using cell strains; that this inhibition depends on the length of the fluorinated carbon chain, rather than the functional groups; and that a longer carbon chain has higher inhibitory actively. The production of monomers using fluorinated long-carbon-chain compounds has been restricted.

Moreover, fluorine-containing alcohols containing a perfluoroalkyl group having 6 or less carbon atoms problematically have insufficient adhesion to inorganic substrates such as glass, metal, and stone.

Patent Documents 1 and 2 indicate that a fluorine-containing alcohol, an alkoxysilane (and a polymerizable functional group-containing alcohol) are subjected to a condensation reaction. However, the resulting alkoxysilane derivatives are used for the preparation of a curable composition to which a photoacid generator or photobase generator is added, or for the preparation of an inorganic conductive coating composition.

PRIOR ART DOCUMENTS PATENT DOCUMENTS

OUTLINE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

An object of the present invention is to provide a composite material of resin - fluorine-containing boric acid composite particles, which does not produce perfluorooctanoic acid, and the like, even when released into the environment, which is formed using a fluorine-containing alcohol having units easily degradable to short-chain compounds, and which has adhesion to inorganic substrates, and the like.

MEANS FOR SOLVING THE PROBLEM

The present invention provides a composite material of resin - fluorine-containing boric acid composite particles comprising a resin, and a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:

        RF-A-OH     [I]

wherein RF is a perfluoroalkyl group having 6 or less carbon atoms, or a polyfluoroalkyl group, in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by a hydrogen atom or hydrogen atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms. The composite material of resin - fluorine-containing boric acid composite particles may be obtained by using a condensate of boric acid, the said fluorine-containing alcohol [I] and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol.

Moreover, the present invention provides a composite material of resin - fluorine-containing boric acid composite particles comprising a resin, and a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:

        RF'-A-OH     [Ia]

or the general formula:

        HO-A-RF"-A-OH     [Ib]

wherein RF' is a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S or N atom; RF" is a linear or branched perfluoroalkylene group containing a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S or N atom; and A is an alkylene group having 1 to 6 carbon atoms. The composite material of resin - fluorine-containing boric acid composite particles may be obtained by using a condensate of boric acid, the said fluorine-containing alcohol [Ia] or [Ib] and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol.

EFFECT OF THE INVENTION

In the fluorine-containing alcohols used in the present invention, the carbon number of the terminal perfluoroalkyl group or the perfluoroalkylene chain in a polyfluoroalkyl group is 6 or less, and units easily degradable to short-chain fluorine-containing compounds are contained. Therefore, the fluorine-containing alcohols do not lead to environmental pollution. Moreover, the resulting composite material of resin - fluorine-containing boric acid composite particles can form a thin film that exhibits excellent water- and oil-repellency and antifouling properties on a substrate surface. This thin film has a resin component, and thus also has excellent adhesion to inorganic substrates, and the like.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

The fluorine-containing alcohol [I] is, for example, a polyfluoroalkyl alcohol represented by the general formula:

        CnF2n+1(CH2)jOH     [II]

The alkylene group A is, for example, a -CH2- group, a -CH2CH2- group, or the like. Examples of the perfluoroalkylalkylalcohol having such an alkylene group include 2,2,2-trifluoroethanol (CF3CH2OH), 3,3,3-trifluoropropanol (CF3CH2CH2OH), 2,2,3,3,3-pentafluoropropanol (CF3CF2CH2OH), 3,3,4,4,4-pentafluorobutanol (CF3CF2CH2CH2OH), 2,2,3,3,4,4,5,5,5-nonafluoropentanol (CF3CF2CF2CF2CH2OH), 3,3,4,4,5,5,6,6,6-nonafluorohexanol (CF3CF2CF2CF2CH2CH2OH), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol (CF3CF2CF2CF2CF2CF2CH2CH2OH), and the like.

Moreover, a polyfluoroalkyl group refers to a group in which the terminal -CF3 group of a perfluoroalkyl group is replaced by, for example, a -CF2H group or a group in which the intermediate -CF2- group is replaced by a -CFH- group or a -CH2- group. Examples of the fluorine-containing alcohol [I] having such a substituent include 2,2,3,3-tetrafluoropropanol (HCF2CF2CH2OH), 2,2,3,4,4,4-hexafluorobutanol (CF3CHFCF2CH2OH), 2,2,3,3,4,4,5,5-octafluoropentanol (HCF2CF2CF2CF2CH2OH), and the like.

The polyfluoroalkyl alcohol represented by the general formula [II] is described, for example, in Patent Document 3, and is synthesized through the following series of steps.

First, a polyfluoroalkyl iodide represented by the general formula:

        CnF2n+1(CF2CF2)b(CH2CH2)cI

is reacted with N-methylformamide HCONH(CH3) to form a mixture of polyfluoroalkyl alcohol and its formate. Then, the mixture is subjected to a hydrolysis reaction in the presence of an acid catalyst to form a polyfluoroalkyl alcohol of the formula:

        CnF2n+1(CF2CF2)b(CH2CH2)cOH

However, the value of n+2b is 6 or less.

Examples of the polyfluoroalkyl iodide include the following:

        CF3(CH2CH2)I

        CF3(CH2CH2)2I

        C2F5(CH2CH2)I

        C2F5(CH2CH2)2I

        C3F7(CH2CH2)I

        C3F7(CH2CH2)2I

        C4F9(CH2CH2)I

        C4F9(CH2CH2)2I

        C2F5(CF2CF2)(CH2CH2)I

        C2F5(CF2CF2)(CH2CH2)2I

        C2F5(CF2CF2)2(CH2CH2)I

        C2F5(CF2CF2)2(CH2CH2)2I

        C4F9(CF2CF2)(CH2CH2)I

        C4F9(CF2CF2)(CH2CH2)2I

The fluorine-containing alcohol [I] may also be a fluorine-containing alcohol wherein the RF group is a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by a hydrogen atom or hydrogen atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, specifically, a polyfluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms, preferably 2 carbon atoms. Examples thereof include polyfluoroalkyl alcohols represented by the general formula:

        CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH     [III]

The polyfluoroalkyl alcohol represented by the general formula [III] is disclosed in Patent Document 3, and synthesized through the following series of steps.

First, a polyfluoroalkyl iodide represented by the general formula:

        CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI

is reacted with N-methylformamide HCONH(CH3) to form a mixture of polyfluoroalkyl alcohol and its formate. The mixture is then subjected to a hydrolysis reaction in the presence of an acid catalyst to form a polyfluoroalkyl alcohol of the formula:

        CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH

Examples of the polyfluoroalkyl iodide include the following:

        CF3(CH2CF2)(CH2CH2)I

        C2F5(CH2CF2)(CH2CH2)I

        C2F5(CH2CF2)(CH2CH2)2I

        C3F7(CH2CF2)(CH2CH2)I

        C3F7(CH2CF2)(CH2CH2)2I

        C4F9(CH2CF2)(CH2CH2)I

        C4F9(CH2CF2)(CH2CH2)2I

        C2F5(CH2CF2)(CF2CF2)(CH2CH2)I

        C2F5(CH2CF2)(CF2CF2)(CH2CH2)2I

        C2F5(CH2CF2)2(CF2CF2)(CH2CH2)I

        C2F5(CH2CF2)2(CF2CF2)(CH2CH2)2I

        C4F9(CH2CF2)(CF2CF2)(CH2CH2)I

        C4F9(CH2CF2)2(CF2CF2)(CH2CH2)I

        C4F9(CH2CF2)(CF2CF2)(CH2CH2)2I

        C4F9(CH2CF2)2(CF2CF2)(CH2CH2)2I

The fluorine-containing alcohol [Ia] is a fluorine-containing alcohol wherein the RF' group is a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S or N atom, specifically, a perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35 carbon atoms, and containing O, S or N, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom. Examples thereof include hexafluoropropene oxide oligomer alcohols represented by the general formula:

        CmF2m+1O[CF(CF3)CF2O]dCF(CF3)(CH2)eOH     [IIa]

Moreover, the fluorine-containing alcohol [Ib] may be a fluorine-containing alcohol wherein the RF" group contains a perfluoroalkylene group having 6 or less carbon atoms, specifically, a perfluoroalkylene group having 5 to 160 carbon atoms, and containing O, S or N, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom. Examples thereof include perfluoroalkylene ether diols represented by the general formula:

        HO(CH2)fCF(CF3)[OCF2CF(CF3)]gO(CF2)hO[CF(CF3)CF2O]iCF(CF3)(CH2)fOH     [IIb]

Among the hexafluoropropene oxide oligomer alcohols represented by the general formula [IIa], a compound wherein m is 1 and e is 1 is described in Patent Document 4, and they are synthesized through the following step.

A fluorine-containing ether carboxylic acid alkyl ester represented by the general formula: CF3O[CF(CF3)CF2O]nCF(CF3)COOR (R: an alkyl group, n: an integer of 0 to 12) is subjected to a reduction reaction using a reducing agent such as sodium borohydride.

Moreover, among the perfluoroalkylene ether diols represented by the general formula [IIb], a compound wherein f = 1 is disclosed in Patent Documents 5 and 6, and they are synthesized via the following series of steps:

        FOCRfCOF → H3COOCRfCOOCH3 → HOCH2RfCH2OH

        Rf:-CF(CF3)[OCF2C(CF3)]aO(CF2)cO[CF(CF3)CF2O]bCF(CF3)-

The alkoxysilane is represented by the general formula:

        (R1O)pSi(OR2)q(R3)r     [IV]

and examples thereof include trimethoxysilane, triethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and the like.

The proportion of these components is such that the boric acid is used at a ratio of about 0.1 to 50 parts by weight, preferably about 10 to 20 parts by weight, based on 100 parts by weight of fluorine-containing alcohol, and such that the alkoxysilane is used at a molar ratio of about 1.0 or less, preferably about 0.05 to 0.50, based on the amount of fluorine-containing alcohol. When the amount of boric acid used is less than this range, water- and oil-repellency decreases. In contrast, when the amount of boric acid used is greater than this range, dispersibility in a solvent decreases. Moreover, when the amount of alkoxysilane used is greater than this range, water- and oil-repellency decreases.

The amount of fluorine-containing alcohol in the obtained fluorine-containing boric acid composite particles is about 25 to 98 mol%, preferably about 40 to 80 mol%. The composite particle size (measured by a dynamic light scattering method) is about 10 to 600 nm, preferably about 15 to 350 nm.

In the fluorine-containing boric acid composite particles obtained as a reaction product, it is considered that the fluorine-containing alcohol is linked to a hydroxyl group of the boric acid particles. Therefore, the chemical and thermal stability of boric acid, and the excellent water- and oil-repellency, antifouling properties, and the like of fluorine are effectively exhibited. In fact, a glass surface treated with the fluorine-containing boric acid composite particles exhibits excellent water- and oil-repellency. Moreover, the particle size of the fluorine-containing boric acid composite particles, and the variation of the particle size show small values. The fluorine-containing boric acid composite particles are formed also as a reaction product of both of a fluorine-containing alcohol and alkoxysilane, and boric acid particles; however, other components are allowed to be mixed as long as the object of the present invention is not impaired.

The fluorine-containing boric acid composite particles are added to a resin to form a composite material. Examples of the resin include thermoplastic resins, such as polymethyl methacrylate, polyethylene, polypropylene, ABS resin, polyamide, polyester, polycarbonate, and polyphenylene sulfide; and thermosetting resins, such as epoxy resin, urethane resin, epoxy acrylate resin, polyimide resin, and unsaturated polyester resin.

The fluorine-containing alcohol, which is a composite component, has no polymer bonds, and thus has inferior durability to washing, etc., and inferior heat resistance. Although a composite of the fluorine-containing alcohol with boric acid has improved durability and heat resistance, its adhesion to inorganic substrates is not sufficient. However, a composite of the fluorine-containing boric acid composite particles with a resin has sufficiently improved adhesion to inorganic substrates.

The fluorine-containing boric acid composite particles may be added at any ratio. For example, in order to modify the resin component, about 1 wt.% of the composite particles based on the resin component can be effective. Moreover, various methods can be used to add the composite particles according to the addition ratio. The fluorine-containing boric acid composite particles can be not only added as one additive, but can also be coated with an organic solvent solution of resin. For example, the addition is performed in the following manner. After a tetrahydrofuran dispersion of a boric acid composite is prepared, a polymethyl methacrylate solution is added dropwise while stirring the dispersion, and tetrahydrofuran is finally added to adjust the concentration.

EXAMPLES

The following describes the present invention with reference to Examples.

Reference Example 1

1,100 mg (3.02 mmol) of CF3(CF2)5(CH2)2OH [FA-6], 200 mg of boric acid and 2 ml of tetrahydrofuran [THF] were charged in a 30-ml reaction vessel, and the mixture was stirred under room temperature condition for a day. Then, the solvent was distilled off, thereby obtaining 767 mg (yield: 59%) of the fluorine-containing boric acid composite particles. With respect to the obtained fluorine-containing boric acid composite particles, the following items were measured.

Particle size and its variation:

The particle size and its variation were measured using a methanol dispersion having a solid matters content of 1 g/L at 25°C by a dynamic light scattering (DLS) method

Reference Examples 2 to 6

In Reference Example 1, the amount of FA-6 was changed appropriately, and tetraethoxysilane [TEOS; density: 0.94 g/cm3] was also appropriately used.

Reference Examples 7 to 16

In Reference Example 1, various fluorine-containing alcohols were used in place of FA-6, and tetraethoxysilane was appropriately used. The amount of THF used in Reference Examples 11 to 13 was 4 ml.

Table 1 Ref. Fluorine-containing alcohol Boric acid TEOS Amount Yield Particle size Example Abbreviation mg mM (mg) ml mM (mg) (%) (nm) 1 FA-6 1100 3.02 200 - - 767 59 130.0±15.0 2 FA-6 1100 3.02 100 - - 900 75 196.0±26.0 3 FA-6 1100 3.02 50 - - 656 57 33.9±5.9 4 FA-6 1100 3.02 200 0.10 0.45 1129 81 54.7± 5.0 5 FA-6 1100 3.02 100 0.10 0.45 1035 80 72.1±17.2 6 FA-6 1100 3.02 50 0.10 0.45 908 73 24.3± 2.4 7 OXF3PO 1250 2.23 60 - - 1061 81 313.0±46.0 8 OXF3PO 1250 2.23 30 - - 1152 90 288.0±78.0 9 OXF3PO 1250 2.23 60 0.10 0.45 1166 89 65.7± 8.9 10 OXF3PO 5600 10.0 30 0.05 0.23 1011 79 266.0±30.0 11 OXF14PO 1000 0.39 6.5 - - 393 39 128.0±14.0 12 OXF14PO 1000 0.39 13 - - 365 36 262.0±59.0 13 OXF14PO 1000 0.39 26 - - 349 34 15.7± 1.0 14 DTFAC 100 0.19 12 - - 108 96 105.0±25.0 15 DTFAC 100 0.19 5.9 - - 103 97 10.8± 1.1 16 DTFAC 100 0.19 2.9 - - 99 96 313.0±78.0

Examples 1 to 8

The fluorine-containing boric acid composite particles (10 mg) obtained in the above Reference Examples were each redispersed in 20 ml of tetrahydrofuran, and 990 mg of polymethyl methacrylate was then added thereto to prepare a polymer composite solution. The solution was coated on a glass substrate to obtain a composite material of resin - fluorine-containing boric acid composite particles. The surface properties of the composite material were analyzed.

Contact angle of droplets (unit: °):

4 µl of droplets of n-dodecane or water were gently brought into contact with thin layer surfaces of the obtained a composite material of resin - fluorine-containing boric acid composite particles, and the contact angle of the droplets adhering to the thin layer surfaces was measured by the θ/2 method using a contact angle meter (Drop Master 300, produced by Kyowa Interface Science Co., Ltd.). The contact angle with water was measured with time. Table2 Reference Water (elapsed time: min.) Example Example n-dodecane 0 5 10 15 20 25 30 1 3 42 100 93 91 92 86 82 77 2 6 38 82 78 78 81 78 80 78 3 7 18 76 72 73 72 74 73 77 4 9 27 92 81 81 76 75 74 72 5 11 53 89 77 83 75 78 75 74 6 14 41 77 73 70 66 65 62 62 7 15 38 74 67 63 59 59 56 55 8 16 40 71 66 60 60 57 56 53
 The above results show that water- and oil-repellency was improved in all cases, except for the elapsed-time of 20 to 30 minutes for water.

Comparative Example 1

With respect to an uncoated glass substrate, the surface properties were analyzed in the same manner as in Example 1.

Comparative Example 2

With respect to a glass substrate coated with boric acid, the surface properties were analyzed in the same manner as in Example 1.

Comparative Example 3

With respect to a glass substrate coated with polymethyl methacrylate, the surface properties were analyzed in the same manner as in Example 1.

Comparative Examples 4 to 8

In Example 1, the same amount (10 mg) of each of the following samples was used in place of the fluorine-containing boric acid composite particles, and 990 mg of polymethyl methacrylate was added thereto to prepare a solution, which was then coated on a glass substrate. The surface properties of the glass substrate were analyzed in the same manner as in Example 1.

However, in Comparative Example 4, FA-6 was not used in Example 1, and 50 mg (0.81 mmol) of boric acid and 0.10 ml (0.45 mmol) of TEOS were used. The amount of the product was 130 mg, and the yield was 90%. Moreover, in Comparative Example 6, boric acid was not used in Example 1, and 1,100 mg (3.02 mmol) of FA-6 and 0.10 ml (0.45 mmol) of TEOS were used. The amount of the product was 763 mg, and the yield was 68%.

The results of the foregoing individual Comparative Examples are shown in the following Table 3. Table3 Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 Com. Ex. 1 0 50 - - - - - - Com. Ex. 2 22 60 - - - - - - Com. Ex. 3 10 58 - - - - - - Com. Ex. 4 20 55 - - - - - - Com. Ex. 5 45 81 79 78 76 75 74 73 Com. Ex. 6 11 36 32 28 21 17 13 7 Com. Ex. 7 42 86 81 82 78 78 77 75 Com. Ex. 8 58 102 81 79 77 76 71 70

 A composite material of resin - fluorine-containing boric acid composite particles comprising:
a resin and a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:

        RF-A-OH     [I]

wherein RF is a perfluoroalkyl group having 6 or less carbon atoms, or a polyfluoroalkyl group, in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by a hydrogen atom or hydrogen atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms, or
comprising:
a resin, and a condensate of boric acid, the said fluorine-containing alcohol and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol. The composite material of resin - fluorine-containing boric acid composite particles according to claim 1, wherein the fluorine-containing alcohol represented by the general formula [I] is a polyfluoroalkyl alcohol represented by the general formula:

        CnF2n+1(CH2)jOH     [II]

wherein n is an integer of 1 to 6, and j is an integer of 1 to 6. The composite material of resin - fluorine-containing boric acid composite particles according to claim 1, wherein the fluorine-containing alcohol represented by the general formula [I] is a polyfluoroalkyl alcohol represented by the general formula:

        CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH     [III]

wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 2, and c is an integer of 1 to 3. The composite material of resin - fluorine-containing boric acid composite particles according to claim 1, wherein the alkoxysilane is a silane derivative represented by the general formula:

        (R1O)pSi(OR2)q(R3)r     [IV]

wherein R1 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group; R2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, with the proviso that not all of R1, R2 and R3 are aryl groups; and p+q+r is 4, with the proviso that q is not 0. The composite material of resin - fluorine-containing boric acid composite particles according to claim 1, wherein the boric acid is used at a ratio of 0.1 to 50 parts by weight based on 100 parts by weight of the fluorine-containing alcohol. A composite material of resin - fluorine-containing boric acid composite particles comprising:
a resin, and a condensate of boric acid and a fluorine-containing alcohol represented by the general formula:

        RF'-A-OH     [Ia]

or the general formula:

        HO-A-RF"-A-OH     [Ib]

wherein RF' is a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S or N atom; RF" is a linear or branched perfluoroalkylene group containing a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S or N atom; and A is an alkylene group having 1 to 6 carbon atoms, or
comprising:
a resin, and a condensate of boric acid, the said fluorine-containing alcohol and an alkoxysilane at a molar ratio of 1.0 or less based on the fluorine-containing alcohol. The composite material of resin - fluorine-containing boric acid composite particles according to claim 6, wherein the fluorine-containing alcohol represented by the general formula [Ib] is a perfluoroalkylene ether diol represented by the general formula:

        HO(CH2)fCF(CF3)[OCF2CF(CF3)]gO(CF2)hO[CF(CF3)CF2O]iCF(CF3)(CH2)fOH     [IIb]

wherein f is an integer of 1 to 3, g+i is an integer of 0 to 50, and h is an integer of 1 to 6. The composite material of resin - fluorine-containing boric acid composite particles according to claim 6, wherein the alkoxysilane is a silane derivative represented by the general formula:

        (R1O)pSi(OR2)q(R3)r     [IV]

wherein R1 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group; R2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, with the proviso that not all of R1, R2 and R3 are aryl groups; and p+q+r is 4, with the proviso that q is not 0. The composite material of resin - fluorine-containing boric acid composite particles according to claim 6, wherein the boric acid is used at a ratio of 0.1 to 50 parts by weight based on 100 parts by weight of the fluorine-containing alcohol. A surface-treating agent comprising the composite material of the resin - fluorine-containing boric acid composite particles according to claim 1 or 6 as an active ingredient. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln, umfassend: ein Harz und ein Kondensat aus Borsäure und einem fluorhaltigen Alkohol, dargestellt durch die allgemeine Formel:

        RF-A-OH     [I]

worin RF eine Perfluoralkylgruppe mit 6 oder weniger Kohlenstoffatomen ist, oder eine Polyfluoralkylgruppe, in welcher ein Fluoratom oder einige der Fluoratome der Perfluoralkylgruppe durch Wasserstoffatom(e) ersetzt ist/sind, und welche eine terminale Perfluoralkylgruppe mit 6 oder weniger Kohlenstoffatomen und eine Perfluoralkylengruppe mit 6 oder weniger Kohlenstoffatomen enthält; und A ist eine Alkylengruppe mit 1 bis 6 Kohlenstoffatom(en), oder umfassend:
ein Harz und ein Kondensat von Borsäure, dem fluorhaltigen Alkohol und einem Alkoxysilan in einem molaren Verhältnis von 1,0 oder weniger, bezogen auf den fluorhaltigen Alkohol. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 1, wobei der durch die allgemeine Formel [I] dargestellte fluorhaltige Alkohol ein Polyfluoralkylalkohol ist, dargestellt durch die allgemeine Formel:

        CnF2n+1(CH2)jOH     [II]

worin n eine ganze Zahl von 1 bis 6 ist und j eine ganze Zahl von 1 bis 6 ist. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 1, wobei der durch die allgemeine Formel [I] dargestellte fluorhaltige Alkohol ein Polyfluoralkylalkohol ist, dargestellt durch die allgemeine Formel:

        CnF2n+1(CH2CF2)n(CF2CF2)b(CH2CH2)cOH     [III]

worin n eine ganze Zahl von 1 bis 6 ist, a eine ganze Zahl von 1 bis 4 ist, b eine ganze Zahl von 0 bis 2 ist und c eine ganze Zahl von 1 bis 3 ist. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 1, wobei das Alkoxysilan ein Silanderivat ist, dargestellt durch die folgende allgemeine Formel:

        (R1O)pSi(OR2)q(R3)r     [IV]

worin R1 und R3 jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Arylgruppe sind; R2 eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Arylgruppe ist, mit der Maßgabe, dass nicht alle von R1, R2 und R3 Arylgruppen sind; und p+q+r ergibt 4, mit der Maßgabe, dass q nicht 0 ist. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 1, wobei die Borsäure in einem Verhältnis von 0,1 bis 50 Gewichtsteilen, bezogen auf 100 Gewichtsteile des fluorhaltigen Alkohols, verwendet wird. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln, umfassend: ein Harz und ein Kondensat aus Borsäure und einem fluorhaltigen Alkohol, dargestellt durch die allgemeine Formel:

        RF'-A-OH     [Ia]

 oder der allgemeinen Formel:

        HO-A-RF" -A-OH     [Ib]

 worin RF' eine lineare oder verzweigte Perfluoralkylgruppe ist, enthaltend eine terminale Perfluoralkylgruppe mit 6 oder weniger Kohlenstoffatomen und eine Polyfluoralkylengruppe mit 6 oder weniger Kohlenstoffatomen, und enthaltend ein O-, S- oder N-Atom; RF" eine lineare oder verzweigte Perfluoralkylengruppe ist, enthaltend eine Perfluoralkylengruppe mit 6 oder weniger Kohlenstoffatomen, und enthaltend ein O-, S- oder N-Atom; und A ist eine Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, oder umfassend:
ein Harz und ein Kondensat aus Borsäure, dem fluorhaltigen Alkohol und einem Alkoxysilan in einem molaren Verhältnis von 1,0 oder weniger, bezogen auf den fluorhaltigen Alkohol. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 6, wobei der durch die allgemeine Formel [Ib] dargestellte fluorhaltige Alkohol ein Perfluoralkylenetherdiol ist, dargestellt durch die allgemeine Formel:

        HO(CH2)fCF(CF3[OCF2CF(CF3)]gO(CF2)hO[CF(CF3)CF2O]iCF(CF3)(CH2)fOH     [IIb]

worin f eine ganze Zahl von 1 bis 3 ist, g+i eine ganze Zahl von 0 bis 50 ist und h eine ganze Zahl von 1 bis 6 ist. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 6, wobei das Alkoxysilan ein Silanderivat ist, dargestellt durch die allgemeine Formel:

        (R1O)pSi(OR2)q(R3)r     [IV]

worin R1 und R3 jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Arylgruppe sind; R2 eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Arylgruppe ist, mit der Maßgabe, dass nicht alle von R1, R2 und R3 Arylgruppen sind; und p+q+r 4 ist, mit der Maßgabe, dass q nicht 0 ist. Verbundmaterial aus Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 6, wobei die Borsäure in einem Verhältnis von 0,1 bis 50 Gewichtsteilen, bezogen auf 100 Gewichtsteile des fluorhaltigen Alkohols, verwendet wird. Oberflächenbehandlungsmittel, umfassend das Verbundmaterial aus den Harz-fluorhaltigen Borsäureverbundpartikeln gemäß Anspruch 1 oder 6 als aktiver Inhaltsstoff. Matériau composite de particules composites résine-acide borique contenant du fluor comprenant : une résine et un condensat d'acide borique et un alcool contenant du fluor représenté par la formule générale :

        RF-A-OH     [I]

dans laquelle RF est un groupe perfluoroalkyle comportant 6 atomes de carbone ou moins, ou un groupe polyfluoroalkyle, dans lequel certains du ou des atomes de fluor du groupe perfluoroalkyle sont remplacés par un atome d'hydrogène ou des atomes d'hydrogène, et qui contient un groupe perfluoroalkyle terminal comportant 6 atomes de carbone ou moins et un groupe perfluoroalkylène comportant 6 atomes de carbone ou moins ; et A est un groupe alkylène comportant 1 à 6 atomes de carbone, ou comprenant :
une résine, et un condensat d'acide borique, ledit alcool contenant du fluor et un alcoxysilane à un rapport molaire de 1,0 ou moins rapporté à l'alcool contenant du fluor. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 1, dans lequel l'alcool contenant du fluor représenté par la formule générale [I] est un poly(alcool fluoroalkyle) représenté par la formule générale :

        CnF2n+1(CH2)jOH     [II]

dans laquelle n est un entier de 1 à 6, et j est un entier de 1 à 6. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 1, dans lequel l'alcool contenant du fluor représenté par la formule générale [I] est un poly(alcool fluoroalkyle) représenté par la formule générale :

        CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH     [III]

dans laquelle n est un entier de 1 à 6, a est un entier de 1 à 4, b est un entier de 0 à 2, et c est un entier de 1 à 3. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 1, dans lequel l'alcoxysilane est un dérivé de silane représenté par la formule générale :

        (R1O)pSi(OR2)q(R3)r     [IV]

dans laquelle R1 et R3 sont chacun un atome d'hydrogène, un groupe alkyle comportant 1 à 6 atomes de carbone ou un groupe aryle ; R2 est un groupe alkyle comportant 1 à 6 atomes de carbone ou un groupe aryle, à condition que R1, R2 et R3 ne soient pas tous des groupes aryles ; et p+q+r vaut 4, à condition que q ne vaille pas 0. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 1, dans lequel l'acide borique est utilisé à un rapport de 0,1 à 50 parties en poids rapporté à 100 parties en poids de l'alcool contenant du fluor. Matériau composite de particules composites résine-acide borique contenant du fluor comprenant : une résine, et un condensat d'acide borique et d'un alcool contenant du fluor représenté par la formule générale :

        RF'-A-OH     [Ia]

ou la formule générale :

        HO-A-RF"-A-OH     [Ib]

dans lesquelles RF' est un groupe perfluoroalkyle linéaire ou ramifié contenant un groupe perfluoroalkyle terminal comportant 6 atomes de carbone ou moins et un groupe perfluoroalkylène comportant 6 atomes de carbone ou moins, et contenant un atome O, S ou N ; RF" est un groupe perfluoroalkylène linéaire ou ramifié contenant un groupe perfluoroalkylène comportant 6 atomes de carbone ou moins, et contenant un atome O, S ou N ; et A est un groupe alkylène comportant 1 à 6 atomes de carbone, ou comprenant :
une résine, et un condensat d'acide borique, ledit alcool contenant du fluor et un alcoxysilane à un rapport molaire de 1,0 ou moins rapporté à l'alcool contenant du fluor. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 6, dans lequel l'alcool contenant du fluor représenté par la formule générale [Ib] est un perfluoroalkylène éther diol représenté par la formule générale :

        HO(CH2)fCF(CF3)[OCF2CF(CF3)]gO(CF2)hO[CF(CF3)CF2O]iCF (CF3)(CH2)fOH     [IIb]

dans laquelle f est un entier de 1 à 3, g+i est un entier de 0 à 50, et h est un entier de 1 à 6. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 6, dans lequel l'alcoxysilane est un dérivé de silane représenté par la formule générale :

        (R1O)pSi(OR2)q(R3)r     [IV]

dans laquelle R1 et R3 sont chacun un atome d'hydrogène, un groupe alkyle comportant 1 à 6 atomes de carbone ou un groupe aryle ; R2 est un groupe alkyle comportant 1 à 6 atomes de carbone ou un groupe aryle, à condition que R1, R2 et R3 ne soient pas tous des groupes aryles ; et p+q+r vaut 4, à condition que q ne vaille pas 0. Matériau composite de particules composites résine-acide borique contenant du fluor selon la revendication 6, dans lequel l'acide borique est utilisé à un rapport de 0,1 à 50 parties en poids rapporté à 100 parties en poids de l'alcool contenant du fluor. Agent de traitement de surface comprenant le matériau composite des particules composites résine-acide borique contenant du fluor selon la revendication 1 ou 6 en tant qu'ingrédient actif. REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description